Condensation products of tri-(betaaminoethyl)-amine and beta-diketones or hydroxy methylene ketones



Patented Feb. 15, 1949 councusn'rron rnonnc'rs or rat-(mere: nsuuoc'rnrm-noime nun corn-numrmms on nynnoxr snzrnrwun lili- TUNES Lyle A. Hamilton.

l'iimnn, and Charles J. Pedersen. l'cuns Grove. N. 3..

asslgnors in E. I. du

I Pent do Ncmonrc 8: Company. Wilmington,

Duh. a corporation of Delaware No Drawing. Appllcaiion June 4. 1947,

Serial No. 152.562

Claims. iGl. 260-566) 2 This invention relates to new chemical cempounds -and more particularly to condensation L I products or trl-(bete-aniinocthyl) -aminc with l i r beta-dilrctones and beta hydroxy leetones.

It is known that many organic products tend to oxidize and deteriorate in the presence of oxygen. Frequently. such organic products become contaminated with. or come into contact with. metals and metal compounds which are active to catalyze the oxidation and deterioration oi such organic products.

It has been proposed to condense various amines with certain ketoues and iiidchydes to produce compounds of the Schiil's base type which are effective to varying degrees in inhibiting the oxidation and deterioration oi organic productsst fi .Some of such compounds are eil'ectivc to inhibit oxidation and deterioration of the organic products in the presence of oxyeen and in the absence of catalytically active metals and their compounds but are substantially ineiicctive in the presence or such catolyticeily active metals. Other com pounds of the Schii't's base type, particularly those derived from certain dianiines and orthohydroxy aromatic aldehydcs. as disclosed in Patent 2.181.12l'tc Downing et at. are eilcctiva to overcome the catalytic cil'cot oi copper and its compounds and are known'es copper deactivators or metal deactivators. Generally. such metal dcactivatore are eiiective to deactivate only one or two metals and, hence, are 0! rather limited usefulness because organic products frequently 1 come into contact with a number of different catalytically active metals. T

It is an oblect oi the present invention to provide new chemical compounds. Another object is to provide new chemical compounds oi the Sohiil's base 'type which are the condensation products of a tri- (beta-aminoethyl) -amine with a beta dllcetcne or a. hydroxy methylene ketone. A further obiect is to provide chemical compounds of the Schlii's base type which are particularly eilective for suppressin the catalytic activity oi most of the metals with which oxidizable organic products are ordinarily brought into contact. Other objects are to advance the art. Still other objects will appear hereinaiter.

The above and other objects oi our invention may be accomplished by providing compounds or the formula.

wherein each cl R. and R represents a member of the group consisting of hydrogen and methyl radicnis. each of X and Y represents a member of the group consisting oi hydrogen and aliryi. arallryl and aryl radicals and Z represents a member of the group consisting oi alkyl. oralkyl and aryl groups. We have found that such compounds may be readily prepared by the condensation oi one moi of a tri-(beta-aminoethyll-omine with three malls of a beta diketone whereby one of the carbonyl groups condenses with the primary amino group and the other carbonyl group is converted to a hydroxy methylene group. The compounds may also he obtained by condensing the amine with a beta-(hydroxy methylene) iretone in place 0! the beta diketone. In general. such compounds are eiiective to suppress the catalytic action oi vanadium. chromium. iron. cobalt. nickel and copper and their catalytically active compounds on the oxidation of oxldlzeble organic products. These compounds are unusual in this respect since most metal denctivators are efiective to suppress the catalytic activity of only one or two oi such metals.

- The amines. from which our compounds are prepared, are the trl-(bete-aminoethyll-omlnes oi the general iormula tmu-on-onin A -01 H. and R in the formula represents hydrogen solely.

The beta dlketencs, employed for producing our compoundmmay be represented by the formula wherein each oi X and Y represents hydrogen or an aikyl. aralkyl. or nryl radical and Zmeprcsents an olkyl. arelkyl. or aryl radical. Preferably. Y represents hydrogen and X and Z represent as. drocarbon radicals and particularly allcyl radicals. The resulting preferred compounds are particu- -tone) tri-(beta-aminoethyll -amine derived frombenaoylacetone.

In place of the beta diketonea, we may employ the corresponding beta-(hydroxy methylene) ketones which may be represented by the formula xo-i=c-o-z l l Particularly desirable beta-(hydroxy methylene) ketones are hydrory methylene acetone and hydroxy methylene oamphor which form tri- (hydroxy methylene acetone) tri-(beta-aminoethyl) -a.mine and tri-(hydroay methylene camphor) tri-(beta-aminoethyD-amine. respectively. The ketones. which may be employed to produce our novel compounds. may contain halogens.

nitrogro mmrgroupssuchas o o --0M and --!--on wherein M is a salt-forming noun or element such as ammonium. lithium. sodium. potassium. and magnesium.

The compounds of our invention include salts wherein the hydrogen atoms of the hydroxy -groups are replaced by metals or other suitable cations such as lithium. sodium. potassium. maenesium. calcium. strontium. barium. zinc. cadmium. tin. ammonium and tetra-silty! ammonium. Some or such salts, such as those of the alkali metals. are water-soluble and are particularly suitable for use in aqueous systems.

The compounds oi this invention are light bud colored products and are generally crystalline and colorless when pure. Many are soluble in water and all iorm-water-soluble salts and are soluble in alcohols. They are euillciently soluble in hydrocarbons. such as gasoline. lubricating oils and the like and in rubber so that they may be dissolved therein in an amount su'ilicient to protect such products against the catalytic action of metals. These compounds may be readily prepared by mixing the amine and the beta-dllretone or beta-(hydroxy methylene) lcetone at room temperatures. Their preparation is usually facilitated by carrying out the reaction in a solvent;

such aswater. dilute aqueous alkali. methanol.

alcohol and the like. The reaction is exothermic and hence it will generally be desirable to add one of the reactants gradually to the other, employing cooling if desired.

As illustrative of such a preparation. tri-(acetylaoetone) tn.-(beta.-amlnoethyl) -amine was prepared by dissolving 14.05 grams of tri-ibeta-ami- .noethyl) -amine trihydrochloride in 20 cc. oi we ter and then adding 6 grams of sodium hydroxide as a 30% aqueous solution and 10 cc. of methanol. To this solution were added 14.6 grams of acetylacetone and the mixture was stirred. The reaction was spontaneous and the resulting product. aiterether extraction. analyzed 14.05% nitrogen (calculated nitrogen= 14.28%)

Compounds of our invention are particularly useiul ior addition to oiridlzable organic products which are brought into contact with or which may be contaminated with catalytically active metals.

accused The amount of the compounds added to the organic materials will be dependent upon the amount of metal catalyst present in the organic materials. Generally. the compounds will be 5 added in an amount equal to about 5 to about times the amount of catalytic metal present.

In order to illustrate the desirable properties or our new compounds. the following example is given: I a

- Exams: ,1

To a cracked gasolinewhlch had been completely reilned but whiclrwas otherwise untreated with chemical scents, such as dyes. antbknoclc and antioxidants. and which had an induction period of 120 minutes, was added 0.002595 of 4- (nbutylaminol -phenol. an antioxidant. whereby the induction period was raised to 8'25 minutes. To dlil'erent samples oi this Baseline. there was added gasoline soluble salts oi the catalytic element (indicated by the chemical symbols of the element) in the indicated concentrations in parts per million of the element. To portions or these samples. there was added 0.005% by weight oi tri- (acetylacetone) tri-(heta aminoethyl)- amine. The induction periods 0! the various samples were then determined by the Voorhees- Elslnzer induction method described in 1.1. a. c. 25, 89'! (1933). The results are given in the following Table I:

Table I Yoorheu-Eisi Induction Period ln fi limtes when disalicylal propyienadiamine was tested in the seine manner as that described above. it was found that while it was eil'ectivo to deactivate copper. it was inedcctive to deactivate chromium or nickel and actually increased the pro-oxidant elects oi mansenese. iron and cobalt. This is illustrative oi the eil'ects obtained with Schiit's base type compounds heretoiore proposed as metal deactivators as in Patents 2,181,121, 2,131, 122. 2,255,597, 2.284.261. 2,285,269 and 2,285,260.

It will thus be apparent that by our invention we have provided a class of new chemical compounds which can be readily prepared. These compounds have novel properties which render them useful and valuable in applications where related compound of the prior art are not applica le.

This is a continuation-impart oi our copendhis application Serial No. 621.280 flied I. 1945. now abandoned.

We claim:

1 A compound oi the formula ('l'li "*i"'i')" 1 wherein each of R. and R. represents a member of the group consisting of hydrogen and methyl radicals. each at X and Y represents a member 0! the group consisting of hydrogen and hydrocarbon radicals and 2 represents a hydrocarbon noun.

2. A compound of the formula November 6 111mm 1! pres-2;: e byes-newton redial and v 8. A compound at the (cumin 2 represents an Ind! Mafia-4W a. 'Iri-(neetyheehone) mam-mm!)- amine.

tAeompaundonhefommln I w flmmlndicnl.

a-o-c-ca-wu-cnr-nnru i CHARLES J. PEDERSEH I wherein X represents an elm radical end 2 repm me cited.

resents an alkyl radial. 1.

Certificate of Correction February 15, 1949.

Patent No. 2,461,894.

Itis hereby certifiegi that error appears in the printed specification o numbered patent requmng correction as follows:

Column 2, lines 27 to 33 inciusive, for the indistinct printed matter insert one or two of such me The amines, from which our c0mpo1mds aminoethyO-amines of the general formula (HzN-CB-CH- N are prepared, are the tr'i-(betmand that the said Letters Patent should be read wit same may conform to the record of the case in the Patent Oifice.

Signed. and sealed this 19th day of April, A. D. 1949.

THOMAS F. MURPHY,

Assistant Gammzssz'oner of Patents.

LYLE A. HAMILTON ET AL. I

f the above h this correction therein that the 

